EP1888658B1 - Nitroxydes polymères, leur synthèse et leurs applications - Google Patents

Nitroxydes polymères, leur synthèse et leurs applications Download PDF

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Publication number
EP1888658B1
EP1888658B1 EP06763310A EP06763310A EP1888658B1 EP 1888658 B1 EP1888658 B1 EP 1888658B1 EP 06763310 A EP06763310 A EP 06763310A EP 06763310 A EP06763310 A EP 06763310A EP 1888658 B1 EP1888658 B1 EP 1888658B1
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Prior art keywords
nitroxide
oxyl
process according
tetraalkyl
formula
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EP1888658A1 (fr
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Peter Nesvadba
Lucienne Bugnon Folger
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BASF SE
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Ciba Holding AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation

Definitions

  • the instant Invention relates to a process for the preparation of polymeric nitroxide radicals by group transfer polymerization. Further aspects of the invention are the polymers containing the nitroxide radicals as well as their use, in particular as active electrode materials in organic radical batteries.
  • the International Publication WO99/28359 describes the radical polymerisation of -N-OH monomers. Polymers comprising a radica N-O' are obtained from N-OH compounds by additional oxidation. In one of the examples the starting material is a homopolymer prepared by anionic polymerization of 4-methacryloyloxy-2,2,6,6,-tetramethyl(piperidin-1yloxyl). The detailed preparation of the polymer is not disclosed.
  • Suitable unsaturated acyl derivatives of nitroxides can be efficiently polymerized by means of G roup T ransfer P olymerization (GTP) to afford polymeric nitroxides having 100% of the theoretical nitroxide content or slightly below if additional crosslinking of the polymer with a nitroxide free crosslinker is performed.
  • GTP G roup T ransfer P olymerization
  • the term slightly below means between 90 and 100 %, preferably 95 and 100% and most preferred between 97 and 100% of the theoretical value based on the nitroxide monomer only.
  • the polymers obtained have nitroxide groups at every repeating unit of the polymer and therefore have 100% theoretic nitroxide content. This quantitative nitroxide content can not be achieved by the oxidation of the corresponding polymeric amines.
  • polymeric nitroxides obtained by GTP particularly suitable for all applications where polymers with a high content of nitroxides per weight of the polymer are required.
  • Typical examples for such applications are the use as stabilizers to prevent degradation of organic materials by heat, oxygen, actinic or electromagnetic radiation, as inhibitors to prevent unwanted polymerization of unsaturated monomers, as active electrode materials in organic radical batteries and as oxidation catalysts.
  • One aspect of the invention is a process for preparing polymeric nitroxides containing one or two nitroxide radicals per repeating unit, which process comprises polymerizing a monomer of formula (I) wherein
  • the polymeric nitroxide contains only 1 nitroxide radical per repeating unit and consequently Q is an open chain or cyclic organic group containing 1 nitroxide radical.
  • the polymerization of the nitroxide, containing monomer under group transfer polymerization conditions results in a polymer with maximum NO- capacity.
  • Q is a heterocyclic 5 or 6-membered radical of formula (II) wherein A is a divalent group required to form a cyclic 5-or 6-membered ring, which may contain additional O or N atoms and the R 101 are independently C 1 -C 6 alkyl or two together with the linking carbon atom form a C 5 -C 6 cycloalkyl group.
  • the R 101 are independently C 1 -C 4 alkyl and the heterocyclic ring is a derivative of a 6-membered tetraalkylpiperidine-N-oxyl, a 3,3,5,5-tetraalkyl-morpholin-2-one-N-oxyl, a 3,3,5,5-tetraalkyl-piperazin-2-one-N-oxy, a 3,3,5,5-tetraalkyl-piperazine-2,6-dione-N-oxyl or a derivative of a 5-membered 2,2,5,5-tetralkyl-2,5-dihydro-1H-pyrrole-N-oxyl, 2,2,5,5-tetraalkyl-pyrrolidine-N-oxyl, 2,2,4,4-tetraalkyl-oxazolidine-N-oxyl or 2,2,5,5-tetraalkylimidazolidin-4-one-N-oxyl.
  • Anspruch 3 is a derivative of a 6-member
  • the monomer is of formula (Ia) wherein
  • R 4 is H.
  • nitroxide containg polymers are of the following structures: polymer from (Ib) wherein R 4 and X have the meaning as defined above and n is number from 10 to 10 000.
  • X is O or NR 2 and R 2 is C 1 -C 4 alkyl, cyclohexyl, benzyl, C 1 -C 8 alkoxycarbonyl or phenyl. (Anspruch 5)
  • the monomer is of formula (Ic)
  • a particularly preferred single monomer compound is 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl.
  • the number average molecular weight M n of the non-crosslinked polymer depends on the amount of initiator used and is typically from 1000 to 1000 000, preferably from 2000 to 200 000 and in particular from 5000 to 50 000.
  • the M n of the crosslinked polymer is higher and its actual value depends on the amount of crosslinker.
  • nitroxide containing monomers are known and can be prepared as for example described in J. Polym. Sci.: Polymer Chemistry Edition 12, 1407(1974 ), GB 2335190 ,( A-21567 ) GB 2342649 ( A-21850 ) or WO 96/24620 . Further suitable nitroxides are described in US-A-4 581 429 or EP-A-621 878 ,.
  • GTP Group transfer polymerization
  • the initiator can be for example (1-methoxy-2-methyl-propenyloxy)-trimethyl-silane but other silylketene acetals may be also used.
  • the silyl ketene acetal initiator can be also formed in situ from the nitroxide monomer using suitable silylating agents, such as for example: trimethylsilyl cyanide, trimethylsilyl chloride or others.
  • the group transfer polymerization is carried out in the presence of a silylketene acetal initiator. (Anspruch 6)
  • the amount of the initiator can be varied broadly. For example 0.01 to 10 mol-%, preferably 0.1 to 5 mol% and more preferably 0.2 to 3 mol%, based on the molar amount of monomer may be used.
  • the ratio [Monomer] / [Catalyst] determines the molecular weight of the target polymeric nitroxide.
  • a variety of catalysts can be used in combination with the initiator.
  • the catalyst is used at about 0.1 -20 mol% based on the molar amount of the initiator, but it can sometimes be used also at higher or lower levels.
  • Lewis acid catalysts such as for example ZnBr 2 , ZnCl 2 , HgCl 2 +J 2 or alkylaluminumchlorides are also suitable as catalysts.
  • the group transfer polymerization is carried out in the presence of a catalyst selected from the group consisting of fluorides, bifluorides, carboxylates, bicarboxylates and Lewis acids. (Anspruch 7)
  • the polymerization can be carried out in many solvents, preferred are aliphatic or aromatic hydrocarbons or ethers, for example tetrahydrofurane (THF), dibutyl ether or methyl-t-butyl ether.
  • solvents preferred are aliphatic or aromatic hydrocarbons or ethers, for example tetrahydrofurane (THF), dibutyl ether or methyl-t-butyl ether.
  • the polymerization can be carried out within a broad temperature range, for example between -100° C and + 100 °C, preferably between 0° C and 80 °C.
  • the reaction time may vary from several minutes, for example 10 minutes up to 20 hours. Typical reaction times are from 1 hour to 15 hours. Usually the reaction is carried out under normal pressure.
  • a suitable polyfunctional GTP polymerizable monomers can be added. These monomers can, depending on their amount and functionality, lead to completely insoluble, crosslinked polymeric nitroxides. The nitroxide content will then be slightly less then 100%, usually between 90% and 100%, but still significantly higher than achievable by direct oxidation of the corresponding precursor amine.
  • polyfunctional monomer means that two or more GTP polymerizable functional groups are present in the monomer.
  • the amount of the polyfunctional GTP polymerizable monomer can be broadly varied, for example within 0.01 -10%, in particular 0.05 - 5%, preferably 0.1-5% based on the weight of the nitroxide containing monomer. (Anspruch 8)
  • Non limiting examples for polyfunctional GTP polymerizable monomers are:
  • the polymeric nitroxide can be isolated by standard procedures, such as for example by precipitation in a suitable solvent.
  • suitable solvents are for example saturated hydrocarbons.
  • Another aspect of the invention is a polymeric nitroxide, containing one or two nitroxide radicals per repeating unit of formula (III) wherein R 1 and Q are as defined above and n is a number from 10 to 10 000, prepared by a GTP process as described above. (Anspruch 9)
  • a further aspect of the invention is the use of a polymeric nitroxide prepared according to the process described above as active electrode material in organic radical batteries. (Anspruch 10)
  • Nitroxide polymers as cathode active materials in organic radical batteries have already been described, for example, in Electrochimica Acta 50, 827 (2004 ). The preparation of 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, its free radical polymerization and subsequent oxidation of the polymer into the corresponding polymeric nitroxide is described.
  • the thus prepared nitroxide polymer does not contain 100% nitroxide radicals in the repeating units, since oxidation of the polymer does not convert all amine functionalities. The polymer does, therefore, not provide the full theoretical capacity for the organic radical battery.
  • nitroxide polymers of the instant invention provide 100% of the theoretical capacity, since all repeating units contain one or two nitroxide radicals. This is a significant advantage over prior art polymers.
  • Yet a further aspect of the instant invention is the use of a polymeric nitroxide prepared as described above to prevent degradation of organic materials by heat, oxygen, actinic or electromagnetic radiation, as inhibitor to prevent unwanted polymerization of unsaturated monomers and as oxidation catalyst. (Anspruch 11)
  • a 250 ml three neck flask equipped with stirrer, thermometer, reflux condenser and argon inlet is charged with carefully dried 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl (12.0g. 0.05 Mol), prepared as described in J. Polym. Sci.: Polymer Chemistry Edition 12, 1407 (1974 ). 50 ml of tetrahydrofurane (THF), freshly distilled from sodium/benzophenone, are added and the flask is filled with argon.
  • THF tetrahydrofurane
  • Nitroxide content UV spectroscopical determination of absorbance at 462 nm of the polymer dissolved in CH 2 Cl 2 at 50.88 mg/10 ml and 100.90 mg/10ml and calculation using the molar extinction coefficient of analytically pure 4-acetoxy-2,2,6,6-tetramethylpiperidine-N-oxyl reference indicated nitroxide content of 100.26%.
  • Example 2 GTP Polymerization of 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl in the presence of 2 mol% ethylene glycol dimethacrylate.
  • the polymerization is carried out as described in Example 1 with the exception that ethylene glycol dimethacrylate (0.201 g, 0.001 mol) is added before the injection of the tetrabutyl-ammonium fluoride solution (0.1 ml, 0.0001 Mol). Poly(4-methacryloyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl) is obtained as a red powder, 12.04 g.
  • GPC polystyrene calibration
  • Example 3 GTP Polymerization of 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl in the presence of 3.9 mol% ethylene glycol dimethacrylate
  • the polymerization is carried out as described in Example 1 with the exception that ethylene glycol dimethacrylate (0.385 g, 0.00194 mol, 3.88 mol%) is added before the injection of tetrabutyl-ammonium fluoride solution (0.1 ml, 0.0001 Mol).
  • the polymerization solution transforms within approximately 10 seconds after the injection of the tetrabutyl-ammonium fluoride solution into a thick gel and its temperature rises from 22°C to 44 °C.
  • Ethyl acetate (400 ml) and methanol (1 ml) are added after 1 h. The gel is crushed by vigorous stirring and the resulting orange suspension is cooled to -60 °C.
  • the solid is isolated by suction filtration and is redispersed in 400 ml ethyl acetate and filtered again.
  • the filter cake is stirred 12 h in 600 ml dichloromethane, the solid is then filtered off and dried at 60 °C/ 100 mbar till constant weight.
  • the polymer is completely insoluble in tetrahydrofurane, methanol, CH 2 Cl 2 , toluene and dimethylformamide.
  • a crosslinked poly(4-methacryloyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl) is obtained as a red powder, 8.25 g.
  • the nitroxide content of this material is calculated to be 94.3%, under the assumption that all crosslinker is incorporated in the polymer.

Abstract

La présente invention concerne un procédé de synthèse de radicaux nitroxyde polymères par polymérisation par transfert de groupe. D'autres aspects de l'invention concernent les polymères contenant les radicaux nitroxyde ainsi que leurs applications, en particulier en tant que matériaux d'électrodes actives dans les accumulateurs à radicaux organiques.

Claims (10)

  1. Procédé pour préparer des nitroxydes polymères, contenant un ou deux radicaux nitroxyde par motif de répétition, ledit procédé comprenant les étapes consistant à :
    polymériser un monomère de formule (I)
    Figure imgb0023
     dans laquelle
    R1 est CH3 ou H ;
    X est O ou NR2
    Q est un groupe organique à chaîne ouverte ou cyclique contenant 1 ou 2 radicaux nitroxyde et R2 est H, un alkyle en C1-C18 ; un cycloalkyle en C5-C12, un benzyle, un (alcoxy en C1-C18)carbonyle ou un phényle ; ou
    R2 a la même signification que Q ;
    dans des conditions de polymérisation par transfert de groupe.
  2. Procédé selon la revendication 1 dans lequel Q est un radical hétérocyclique
    de 5 ou 6 chaînons de formule (II)
    Figure imgb0024
     dans laquelle A est un groupe divalent requis pour former un cycle de 5 ou 6 chaînons cycliques, qui peut contenir des atomes O ou N additionnels et les groupes R101 sont indépendamment un alkyle en C1-C6 ou deux d'entre eux conjointement avec l'atome de carbone de liaison forment un groupe cycloalkyle en C5-C6.
  3. Procédé selon la revendication 2 dans lequel les groupes R101 sont indépendamment un alkyle en C1-C4 et le cycle hétérocyclique est un dérivé d'un tétraalkylpipéridine-N-oxyle à 6 chaînons, un 3,3,5,5-tétraalkyl-morpholin-2-one-N-oxyle, un 3,3,5,5-tétraalkyl-pipérazin-2-one-N-oxyle, un 3,3,5,5-tétraalkyl-pipérazine-2,6-dione-N-oxyle ou un dérivé d'un 2,2,5,5-tétraalkyl-2,5-dihydro-1H-pyrrole-N-oxyl de 5 chaînons, 2,2,5,5-tétraalkyl-pyrrolidine-N-oxyle, un 2,2,4,4-tétraalkyl-oxazolidine-N-oxyle ou un 2,2,5,5-tétraalkyl-imidazolidin-4-one-N-oxyle.
  4. Procédé selon la revendication 1 dans lequel le monomère est de formule (Ia)
    Figure imgb0025
     dans laquelle
    X est O ou NR2 ;
    R2 est un alkyle en C1-C18 ; un cycloalkyle en C5-C12, un benzyle, un (alcoxy en C1-C18)carbonyle ou un phényle ; et
    R4 est CH3 ou H.
  5. Procédé selon la revendication 4 dans lequel le monomère est de formule (Ib)
    Figure imgb0026
     X est O ou NR2 et R2 est un alkyle en C1-C4, un cyclohexyle, un benzyle, un (alcoxy en C1-C8)carbonyle ou un phényle.
  6. Procédé selon la revendication 1 dans lequel la polymérisation par transfert de groupe est effectuée en présence d'un initiateur d'acétal de silylcétène.
  7. Procédé selon la revendication 1 dans lequel la polymérisation par transfert de groupe est effectuée en présence d'un catalyseur choisi dans le groupe constitué de fluorures, de bifluorures, de carboxylates, de bicarboxylates et d'acides de Lewis.
  8. Procédé selon la revendication 1 dans lequel un monomère polyfonctionnel additionnel est ajouté en une quantité de 0,01 à 10 % en poids sur la base du poids du monomère contenant un nitroxyde.
  9. Utilisation d'un nitroxyde polymère contenant un ou deux radicaux nitroxyde par motif de
    répétition de formule (III)
    Figure imgb0027
     dans laquelle R1 et Q sont comme défini dans la revendication 1 et n est un nombre de 10 à 10 000,
    préparé par un procédé selon la revendication 1,
    en tant que matériau actif d'électrode dans des batteries à radicaux organiques.
  10. Utilisation d'un nitroxyde polymère contenant un ou deux radicaux nitroxyde par motif de
    répétition de formule (III)
    Figure imgb0028
     dans laquelle R1 et Q sont comme défini dans la revendication 1 et n est un nombre de 10 à 10 000,
    préparé par un procédé selon la revendication 1,
    en tant que stabilisant pour prévenir la dégradation de matériaux organiques par la chaleur, l'oxygène, un rayonnement actinique ou électromagnétique, en tant qu'inhibiteur pour prévenir la polymérisation indésirable de monomères insaturés et en tant que catalyseur d'oxydation.
EP06763310A 2005-06-08 2006-05-29 Nitroxydes polymères, leur synthèse et leurs applications Not-in-force EP1888658B1 (fr)

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EP05104974 2005-06-08
PCT/EP2006/062651 WO2006131451A1 (fr) 2005-06-08 2006-05-29 Nitroxydes polymères, leur synthèse et leurs applications
EP06763310A EP1888658B1 (fr) 2005-06-08 2006-05-29 Nitroxydes polymères, leur synthèse et leurs applications

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JP (1) JP2008545863A (fr)
KR (1) KR20080017453A (fr)
CN (1) CN101193924A (fr)
AR (1) AR055966A1 (fr)
AT (1) ATE435877T1 (fr)
CA (1) CA2609982A1 (fr)
DE (1) DE602006007702D1 (fr)
MX (1) MX2007015527A (fr)
TW (1) TW200708524A (fr)
WO (1) WO2006131451A1 (fr)

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JP5176130B2 (ja) * 2007-05-09 2013-04-03 日本電気株式会社 ポリラジカル化合物、電極活物質および電池
WO2008155247A1 (fr) * 2007-06-19 2008-12-24 Basf Se Matériaux d'électrode contenant du nitroxyde pour piles rechargeables
JP4637293B2 (ja) * 2008-07-03 2011-02-23 Ｄｉｃ株式会社 二次電池およびその導電補助層用カーボンインキ
WO2020017630A1 (fr) * 2018-07-19 2020-01-23 日本電気株式会社 Batterie secondaire utilisant un polymère radicalaire dans une électrode

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DE602006007702D1 (de) 2009-08-20
CN101193924A (zh) 2008-06-04
TW200708524A (en) 2007-03-01
WO2006131451A1 (fr) 2006-12-14
US20090137758A1 (en) 2009-05-28
CA2609982A1 (fr) 2006-12-14
EP1888658A1 (fr) 2008-02-20
ATE435877T1 (de) 2009-07-15

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